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WO1997003103A1 - Polymeres phenoliques prepares par des reactions d'aralkylation - Google Patents

Polymeres phenoliques prepares par des reactions d'aralkylation Download PDF

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Publication number
WO1997003103A1
WO1997003103A1 PCT/US1996/011223 US9611223W WO9703103A1 WO 1997003103 A1 WO1997003103 A1 WO 1997003103A1 US 9611223 W US9611223 W US 9611223W WO 9703103 A1 WO9703103 A1 WO 9703103A1
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WIPO (PCT)
Prior art keywords
phenol
styrene
polymer
butyl
mixed
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PCT/US1996/011223
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English (en)
Inventor
David A. Hutchings
Jeffrey L. Mills
Kenneth Bourlier
Original Assignee
Georgia-Pacific Resins, Inc.
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Publication date
Application filed by Georgia-Pacific Resins, Inc. filed Critical Georgia-Pacific Resins, Inc.
Priority to DE69617017T priority Critical patent/DE69617017T2/de
Priority to AT96923613T priority patent/ATE208798T1/de
Priority to AU64082/96A priority patent/AU6408296A/en
Priority to EP96923613A priority patent/EP0837892B1/fr
Priority to JP50587297A priority patent/JP4151748B2/ja
Publication of WO1997003103A1 publication Critical patent/WO1997003103A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes

Definitions

  • This invention is directed to the formation of phenol aralkylation polymers.
  • the polymers produced in accordance with the present invention release negligible phenol and formaldehyde emissions.
  • the polymer class within the scope of the present invention exhibits unique compatibility with oils and alkyd coating systems as well as a broad range of polymer systems including urethanes, epoxies, acrylates, and others which show performance benefits from the additions of phenolics and related aromatic components.
  • Phenolics are used to upgrade corrosion properties, improve adhesion, and improve substrate wetting. They can be "cooked” with various drying oils or simply cold blended with oils or alkyds to produce spar varnishes and metal primers. Although phenolics having some excellent performance properties, such as excellent adhesion and good corrosion properties, other properties are not so desirable. Phenolics have a relatively high viscosity which excludes their use in very low V.O.C. applications.
  • phenolics turn dark in color upon aging which limits their use in some primer and most topcoat systems because of color bleed-through.
  • the use of phenolics in exterior metal paints is limited to primers since the phenolics in such coatings darken (bleed through) with time, changing the color of light topcoats.
  • topcoats must be dark in color in order to not show bleed-through.
  • primers are red or gray. It is believed that darkening upon aging is caused by the formation of quinone methides in the phenolic polymer.
  • Phenolics having lower solution viscosities are desired in order to reduce solution viscosities in spar varnishes, bridge paints, porch and deck enamels, and government specification paints.
  • Phenolics are generally used in conjunction with oils or alkyds for exterior primers. Due to environmental pressures and the commercialization of new polymer systems such as urethanes, these types of phenolics represent a shrinking market.
  • phenolic resins for oils and alkyds are novolak polymers based on substituted phenols. Originally, they were based on 7-phenyl-phenol. This monomer offered a preferred combination of oil solubility, color retention and corrosion resistance.
  • /7-t-butyl phenol formaldehyde polymer The physical properties of the /?-t-butyl phenol resins are not as good as those of the p-phenyl phenol based resins.
  • the ?-t-butyl phenol imparts good oil solubility and limits color body formation when compared to other types of phenols.
  • the methylene linkages allow the formation of quinone methides. It is the presence of quinone methides which is a major reason why the polymers will darken over time. It is believed that the phenyl group has better performance properties when compared to an alkyl group.
  • the present invention is directed to the formation of a class of phenol aralkylation polymers which exhibit improved oil solubility, improved compatibility with oil and alkyd-based polymers, as well as urethanes, epoxies and acrylates and a decreased tendency for color body formation and resultant darkening of coatings in which they are incorporated.
  • the polymers can be made free of formaldehyde and phenol.
  • the present invention is directed to the formation of a phenol aralkylation polymer by aralkylating a phenolic monomer with at least one styrene derivative to obtain an aralkylated phenol, then reacting the aralkylated phenol with an aryl diolefin to obtain the phenol aralkylation polymer, with the aralkylated phenol joined to the aryl diolefin.
  • Those skilled in the art will recognize the primary linkage is at the ortho position. This process produces a lower melting point polymer.
  • the present invention is also directed to the formation of a phenol aralkylation polymer by reacting a phenolic monomer with an aryl diolefin to obtain a phenol/aryl diolefin polymer and then aralkylating the phenol/aryl diolefin polymer with at least one styrene derivative to obtain phenol aralkylation polymer, with a portion of the phenolic component joined to the aryl diolefin with a portion of the phenolic linkages being p in orientation. This process produces a higher melting point polymer.
  • the present invention is directed to a class of phenol aralkylation polymers which impart good oil solubility, limit color body formation and show a decreased tendency to darken over time.
  • the phenol aralkylation polymers of the present invention evolve low phenol and formaldehyde emissions, and have excellent adhesion and corrosion properties.
  • the products of the invention have high solubility in non-aromatic (Hazardous Air Pollutants ("HAP's") free) solvents.
  • HAP's non-aromatic
  • the incorporation of an aryl diolefin into a phenolic polymer results in the formation of polymer systems useful for incorporation with many other polymers which include but are not limited to urethane, epoxy, and acrylate polymer systems.
  • the increase in aromatic character of the phenolic polymer results in an enhancement in their ranges of compatibility with the aforementioned polymer class, and also generally leads to the enhancement of physical properties, adhesion, and barrier property performance.
  • the phenol aralkylation polymers of the present invention are derived from a phenolic monomer, at least one styrene derivative and an aryl diolefin.
  • styrene derivative and aryl diolefin In addition to the phenolic monomer, styrene derivative and aryl diolefin, other reactants may be introduced to produce a product with particular properties.
  • the phenol aralkylation polymers are produced by a process having at least two reaction steps.
  • the order of the reaction of the three reactants is arranged to provide a phenol aralkylation polymer product having desired properties. For instance, at least one styrene derivative is reacted with a phenolic monomer and then the product thereof is reacted with an aryl diolefin. Alternatively, a phenol monomer is reacted with an aryl diolefin, and then the product thereof is reacted with at least one styrene derivative. Similarly, a portion of either the styrene or aryl diolefin may be withheld for later reaction to achieve a predetermined polymer composition exhibiting a desired performance characteristic. Reactants
  • the styrene derivatives may be any of the aryl substituted alkene hydrocarbons. Examples include styrene, ⁇ -methyl styrene, p-me yl styrene, p-t- butyl styrene, ⁇ -methyl-/>-methyl styrene, 3-methyl styrene, tn-ethyl styrene, p- etiiyl styrene, >-vinyl toluene, mixed vinyl toluenes, mixed t-butyl styrenes, mixed ethyl styrenes, mixed t-butyl styrenes with di-t-butyl styrenes, isopropenyl naphthalene, 2-methyl- 1,1 -diphenyl propene, 1 -phenyl- 1-pentene, and the like.
  • Mixed styrene derivatives means a mixture of, for example, p- and m- t-butyl styrenes.
  • the preferred styrene derivatives are styrene and homologs of styrene of the formula
  • Ar may be phenyl, naphthyl, biphenyl, or substituted phenyl, naphthyl, or biphenyl.
  • substitutions may be:
  • R, and R 5 are independently methyl, ethyl, C 3 to C, 0 alkyl, or a halogen.
  • R j , R 2 and R 3 are independently hydrogen, an alkyl radical containing 1 to 5 carbon atoms, an aromatic or an alkyl aromatic.
  • Rtent R 2 and R 3 can be other functionalities such as a carboxyl as in the case of cinnamic acid.
  • esters of styrene derivatives may also be used.
  • R,, JR 2 and R 3 can be carboxyl (- CO 2 H) or alkoxy (-O-R) groups.
  • the styrene derivative is styrene, ⁇ -methyl styrene, /7-t-butyl styrene, -ethyl styrene, p-et yl styrene, p-vinyl toluene, mixed vinyl toluenes, mixed t-butyl styrenes, mixed ethyl styrenes, mixed t-butyl styrenes with di-t-butyl styrenes, or mixtures thereof.
  • the aryl diolefin can be represented by the following formula
  • Ar is benzene, naphthalene, or biphenyl;
  • R I0 , R ⁇ and R i2 independently are a hydrogen or an alkyl radical containing 1-5 carbon atoms.
  • the orientation on the benzene ring is meta or para or mixtures thereof.
  • naphthalene Possible substitutions for naphthalene include 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 2-4, 2-5, 2-6, 2-7 or 2-8 and corresponding mixtures thereof.
  • biphenyl Possible substitutions for biphenyl include 1-3, 1-2', 1-1', 1-3', 2-3', and 3-3', and corresponding mixtures thereof.
  • the aromatic nucleus may be substituted with various R groups, for example, methyl and t-butyl.
  • the aryl diolefin is - or -diisopropenyl benzene (DIPB) or their m, p mixtures or mixed m/p divinylbenzene (DVB) of any of the commercially available concentrations.
  • DIPB diisopropenyl benzene
  • /n-DIPB is commercially available at a 98% concentration.
  • DVB is available at concentrations of, for example, 53%, 62%, and 80%. DVB concentrations also contain ethyl-styrene (vinyl ethyl benzene). For instance, 80% DVB contains approximately 20% ethyl styrene.
  • Diols derived from DIPB such as m or p diols of diisopropyl benzene are acceptable diolefin materials.
  • Diols derived from DIPB such as m or p diols of diisopropenyl benzene are acceptable precurser materials for aryl diolefins since they can be considered blocked aryl diolefins.
  • All or a portion of the styrene derivatives or aryl diolefin may be produced in situ by dehydration of methyl benzylic alcohols at reaction temperatures above 100°C and acidities sufficient to promote dehydration of the benzylic alcohols.
  • the resulting styrene derivative or aryl diolefin may be reacted with a phenolic monomer.
  • Other means to produce the reactants in situ that are within the skill of the art are within the scope of the present invention.
  • the phenolic monomers include phenols which contain at least two free reactive positions.
  • monomers contain at least two free reactive (ortho- or para-positions).
  • free reactive ortho- or para-positions.
  • examples include phenol itself, o-, p- and m-cresol, m-isopropyl phenol, 3,5-xylenol, 3,5- diisopropyl phenol and mixtures of these compounds.
  • Specific classes include:
  • Phenolic monomers containing mononuciear phenolic substituents are shown by the formula:
  • R may be methyl, ethyl, isopropyl, n-propyl, t-butyl, isobutyl, n-butyl, 5-10 aliphatic substituents, phenyl, or a substituent derived from aralkylation with styrene derivatives, e.g styrene, p- methyl styrene, t-butyl styrene, mixed t-butyl styrenes, ⁇ -methyl styrene, and vinyl toluenes.
  • styrene derivatives e.g styrene, p- methyl styrene, t-butyl styrene, mixed t-butyl styrenes, ⁇ -methyl styrene, and vinyl toluenes.
  • Polyhydroxy mononuciear and polynuclear phenolic monomers include:
  • substitutions of R, and R 2 on the ring include 2,3; 2,5; and 2,6, and Ri and R 2 , independently, can be hydrogen, alkyl having 1-10 carbon atoms, and aralkyl derived from styrenes as benzylic derivatives, as previously described.
  • Rj and R 2 can also be divinyl aromatics, which can give rise to chain extended systems, as taught herein, for monohydroxy phenolic monomers. The latter system advantageously requires minimal incorporation of the dihydroxy monomer into the polymeric product to achieve the desired high hydroxy functionality.
  • R is in the 2, 4, or 5 position on the ring.
  • R can be hydrogen, alkyl having 1-10 carbon atoms, aralkyl derived from styrenes or benzylic derivatives, as previously described.
  • R can be divinyl aromatic, which can give rise to chain extended systems, as taught for the monohydroxy phenolic monomers. Advantages of the latter systems include minimal incorporations of tiie subject monomer into an alkylation polymer to achieve the desired high hydroxy functionality.
  • Resorcinol can also be used in the disubstituted (alkyl or aralkyl) mode to produce lower functionality polymers and in combination with difunctionally reactive monomers such as hydroquinone or monosubstituted phenolics, as described herein.
  • substitutions of R, and R 2 on the ring include 3,4 or 3,5 and wherein R j and R 2 , independently, can be hydrogen, alkyl having 1-10 carbon atoms, aralkyl derived from styrenes, or benzylic derivatives, as previously described. R j and R 2 can also be divinyl aromatics, which can give rise to chain-extended systems, as taught for the monohydroxy phenolics. The latter system also advantageously requires minimal incorporation of the dihydroxy monomer into the polymeric product to achieve the desired high hydroxy functionality.
  • Alkyl or aralkyl, substituted polyhydroxy-polycyclic aromatic phenols include:
  • the phenolic monomers may be employed as an initial phenolic monomer in the reaction or may be employed as an additional phenolic monomer later in the reaction. Whether the phenolic monomer is used at an initial stage or as an additional component depends on the particular reaction scheme employed as discussed later.
  • Preferred initial phenolic monomers are phenol, bisphenol A and bisphenol F.
  • Other preferred phenolic monomers include -t-butyl phenol, p- cumyl phenol, and -octyl phenol which may be used as initial phenolic monomers or additional phenolic monomers depending on the particular reaction scheme employed. Polymers produced from the above monomers may also be used as the phenolic monomer.
  • the aryl diolefin is used at a range of mole ratios relative to the phenoiic component.
  • the mole ratio of aryl diolefin to phenolic component may be from 0.2: 1 to 1.1:1.
  • the mole ratio > 1 is used under circumstances in which alkyl or aralkyl substituted phenolics are used and in which high molecular weight product is desired.
  • the lower end of the mole ratio range is employed under circumstances where a low level of chain extension is required.
  • the amount of aryl diolefin also depends on the amount of phenolic hydroxy substitution on the phenolic prepolymer or monomer used.
  • aryl diolefin may be required to give a desired degree of phenolic functionality, because the monomer is higher in both molecular weight and functionality to start with.
  • a formaldehyde-linked phenolic polymer can be further coupled with aryl diolefins to build molecular weight to desired levels.
  • an aralkylation polymer formed from phenolic and aryldiolefin components can be further increased in molecular weight by reaction with formaldehyde under the conditions used to prepare the aralkylation system.
  • a prefe ⁇ ed range of mole ratio is 0.4: 1 to 0.8:1.
  • the degree of styrenation employed with this polymer class can also vary.
  • the degree of styrenation is defined as the ratio between the moles of styrene derivatives used and the molar equivalent of open reactive positions per phenolic monomeric component.
  • the degree of styrenation is determined by subtracting the number of reactive positions used to couple with the aryl diolefin or other linking group from the total number of reactive positions per monomers. For example, phenol is considered to have 3 reactive positions. If two phenol molecules are coupled with an aryl diolefin, two open positions remain per phenol ring.
  • the theoretical mole ratio for styrenation (moles of styrene per phenol molecule) is therefore 2.
  • the effective range for styrenation is from 20 to 100 percent of the theoretical mole ratio with the most effective range being 40 to 95 percent of theoretical. Process
  • One embodiment of the present invention is directed to the formation of a phenol aralkylation polymer by aralkylating a phenolic monomer with at least one styrene derivative to obtain an aralkylated phenol, then reacting the aralkylated phenol with an aryl diolefin to obtain the phenol aralkylation polymer, v/ith the aralkylated phenol joined to the aryl diolefin.
  • aralkylation polymer by aralkylating a phenolic monomer with at least one styrene derivative to obtain an aralkylated phenol, then reacting the aralkylated phenol with an aryl diolefin to obtain the phenol aralkylation polymer, v/ith the aralkylated phenol joined to the aryl diolefin.
  • a phenolic monomer and at least one styrene derivative are reacted in the presence of an acid catalyst.
  • the pH of the reaction mixture is lowered by means of acid catalyst addition. Since the system is generally low in water content, the effective acidity of the catalyst system is increased.
  • Acid catalysts which may be used include but are not limited to:
  • Phenol sulfonic and sulfonated phenolic polymers which may include aralkylated phenolics;
  • Latent acid catalyst systems including organic acid chlorides, phosphorous oxychlorides, and the like;
  • Latent acid catalysts derived from amines and the above;
  • Halogenated organic acids such as chloroacetic and trifluoroacetic acid.
  • the amount of acid catalyst required depends on the effective acidity and type of catalyst selected. Strong acids such as sulfonic and methane sulfonic require quantities less than 0.20 percent based on the total reactive charge providing that said reactants do not contain basic impurities. It will be noted that dilute solutions of said acids can be used providing that provisions are made to remove water from the reaction mixture. Weaker acids require the use of larger quantities (quantities of catalyst) with those skilled in the art being familiar with methods for optimization.
  • the temperature of the reaction depends on a number of factors and is preferably between 120-160°C
  • the temperature selected depends on the nature of the aralkylating agent and requires optimization for each system. In some instances, high temperatures are desired to insure against ⁇ -aralkylation of the phenolics or in others lower temperatures are desirable to minimize retroaralkenylation with the resultant formation of undesired arylolefin coupling products.
  • the reaction time required can vary significantly, but is generally achieved in the 10-30 minute time frame at the average (140°C) reaction temperature.
  • This combination of conditions can be applied to all combinations of phenol, substituted phenols, and phenol aralkylation products with either styrene, its derivatives, or aryldiolefins. It is worth noting that the aralkylation reaction is stopped completely by neutralization of the acid catalyst, and that systems so stabilized can be heated to temperatures in the 200-250°C range for substantial periods without de-aralkylations or other similar decompositions.
  • the phenolic monomer is selected to provide an aralkylated phenol and is preferably phenol, bisphenol A or bisphenol F. Additional phenolic monomers may be added prior to reacting the aralkylated phenol with the aryl diolefin such as /M-butyl phenol, ⁇ -cumyl phenol and /7-octyl phenol. It is within the skill of the art to determine what phenolic monomers are appropriate to react with the styrene derivative to obtain an aralkylated phenol and what phenolic monomers may be added later to build the polymer.
  • the aralkylated phenol product is then reacted with an aryl diolefin to obtain the phenol aralkylation polymer, with the aralkylated phenol joined to the aryl diolefin primarily at the ⁇ -position.
  • the pH of the reaction mixture is lowered by means of acid catalyst addition.
  • the same catalysts can be considered for diolefin reaction with the styrenated phenols as were used to promote the reaction of phenol or its derivatives with arylolefins. Indeed, in practice of this invention, the same catalyst system is normally used to conduct the divinyl aromatic-phenolic polymerization reaction as was used for the precursor phenolic reactant styrenation.
  • the final product can be neutralized with caustic, potassium hydroxide, or generally any alkaline material.
  • the aralkylated phenol product is missing a hydroxyl group and thus does not have the poor compatibility with oils or solvents that are exhibited by bisphenol A.
  • aralkylated phenol is then reacted with /rz-diisopropenylbenzene.
  • Another embodiment employing this reaction scheme initially reacts a phenolic monomer with two styrene derivatives. For example, bisphenol A is reacted with t-butylstyrene and ⁇ -methyl styrene.
  • the styryl substituted bisphenol A systems can be further reacted with divinyl aromatics to achieve chain-extended polymer systems useful in coating and other applications. These systems have good solubility in mineral spirits.
  • Another embodiment of the present invention is directed to the formation of a phenol aralkylation polymer by reacting a phenolic monomer with an aryl diolefin to obtain a phenol/aryl diolefin polymer and then aralkylating the phenol/aryl diolefin polymer with at least one styrene derivative to obtain the phenol aralkylation polymer, with the phenol joined to the aryl diolefin, as those skilled in the art will recognize, primarily at the ortho and para positions.
  • a phenol and an aryl diolefin are reacted to form a phenol/diolefin polymer.
  • the pH of this reaction mixture is lowered by means of acid catalyst additions.
  • the same catalyst systems and processing conditions are required for these embodiments as were described earlier for aralkylation of the unsubstituted phenolic systems using styrene or substituted styrenes.
  • the phenol/diolefin polymer is then aralkylated with a styrene derivative in the presence of an acid catalyst to obtain the phenol aralkylation polymer.
  • the same acid catalysts can be considered for styrene aralkylation of the above phenol aralkylation polymer as were used to react the aryldiolefin with the phenolic reactant. Indeed, in practice of this invention, the same catalyst is used to catalyze both the styrene and diolefin reactions with phenol and its derivatives.
  • the final product can be neutralized with caustic, potassium hydroxide, or an amine or generally any alkaline material compatible in the system.
  • the phenol/diolefin polymer is then reacted with ⁇ -methyl-styrene.
  • Polymers produced by initially reacting a phenol with an aryl diolefin generally result in higher melting point polymers than those produced by reaction of the aryldiolefin with preformed para styrenated phenolics.
  • Another example employing this reaction scheme reacts phenol and diisopropenylbenzene as above, and then further reaction with /?-t-butyl styrene to provide a high melting point (95-105°C versus 35-45°C for similar 7-styrenated phenolic based polymers), phenol aralkylation polymer depicted below and having good mineral spirits solubility.
  • the acid catalyst may be any effective acid catalyst and is preferably methane sulfonic acid.
  • the catalyst systems described earlier may be employed with advantage depending on the results desired.
  • mineral acids may represent the most desired catalyst.
  • sulfuric or phosphoric acid are readily removed as their sodium or potassium neutralization salts.
  • organic neutralization salts may be of an advantage by allowing their retention in the final product as a dissolved phase, the use of organic hydrophobic catalysts such as the alkyl naphthalene sulfonic acids and their amine neutralization products may be of an advantage.
  • Amines can be selected from the group including primary, secondary and tertiary aliphatic (Cj-C, 0 ) and aralkyl amines in which the amine substituents can be aromatic or benzylic in combination with aliphatic components (Cj to C 10 ).
  • a good neutralizing amine for pu ⁇ oses of these products would be diethyltertiary butyl amine.
  • Another embodiment of the present invention reacts the phenolic monomer with a portion of the aryl diolefin, and then reacts the remaining aryl diolefin after aralkylating the phenol with the styrene derivative.
  • Polymers produced in this manner have advantages such as minimizing the potential for gel formation.
  • the present invention produces a resin with low monomer content ( ⁇ 1 percent and excellent yields without the use of formaldehyde.
  • formaldehyde may be added at any stage of the reaction to increase phenol monomer linking.
  • An aralkylation reaction including the addition of formaldehyde is demonstrated below.
  • phenol is aralkylated with ⁇ -methylstyrene.
  • a phenol aralkylation polymer is formed by reacting 1 mole of bisphenol A with from about 0.3 to 0.8 moles of an aryl diolefin to obtain a bisphenol A/aryl diolefin polymer and then aralkylating the polymer with at least one styrene derivative selected from the group consisting of /?-t-butyl styrene, t-butyl styrene, vinyl toluene, ⁇ -methyl styrene, and styrene wherein from 20 to 100 percent of the open reactive sites of the polymer are occupied by styrene derived moieties.
  • styrene derivatives may be reacted with the bisphenol A prior to reacting with the aryl diolefin providing that adequate open reactive positions are retained, a mixture of an aryl diolefin and styrene derivatives may be coreacted with the bisphenol A and/or a portion of the bisphenol A may be replaced with t-butyl phenol.
  • a phenol aralkylation polymer is formed by reacting an aryl diolefin with phenol at a mole ratio of aryl diolef ⁇ n:phenol from about 0.4: 1 to 1.0: 1 to form a phenol/aryl diolefin polymer and then reacting the polymer with at least one styrene derivative selected from the group consisting of -t-butyl styrene, t-butyl styrene, vinyl toluene, styrene, ⁇ -methyl styrene wherein from about 20 to 100 percent of the open reactive sites of the polymer are occupied by styrene derived moieties.
  • styrene derivatives may be reacted with the phenol prior to reacting with the aryl diolefin, formaldehyde may be reacted with the polymer to increase molecular weight and reduce residual phenolic monomer levels, and/or a portion of the phenol may be replaced with t-butyl phenol.
  • styrenated aralkylation phenolic polymers described herein can also be reacted with formaldehyde under basic conditions to generate resole systems having unique solubilities and other related performances advantages.
  • -t-butyl- styrene or a combination of / t-butyl-styrene with ⁇ -methyl-styrene or vinyl toluene are prefe ⁇ ed.
  • solubility of the following examples was determined using a 50 wt% solution of the phenol aralkylation polymer in a 5% n-butanol/mineral spirits solution.
  • a glass-lined reactor was purged with nitrogen. 188 g phenol and 0.6 g methane sulfonic acid catalyst were charged to the reactor and the mixture was heated to 120° C. An equal molar quantity (236 g) of ⁇ -methyl styrene was slowly added while maintaining the temperature. The reaction was exothermic and proceeded quickly. After this reaction had taken place, (130 g) diisopropenylbenzene (DIPB) was slowly added while continuing to keep the temperature at 120°C. Since the para position was the primary site of aralkylation for the initial reaction step, the main position for the diisopropenylbenzene to react was at an ortho position. This reaction was slower than the previous aralkylation.
  • DIPB diisopropenylbenzene
  • the CK-2500 had the lowest color. When used to produce a resin, the CK-2500 tended to discolor more than the other materials.
  • the Mead resin and the inventive resin each had higher molecular weight and a lower solution viscosity than the CK-2500. Low viscosity was a definite advantage when formulating low V.O.C. products. Low viscosity means less solvents required.
  • the reaction was run under a nitrogen atmosphere to minimize color pickup.
  • Bisphenol A was melted in a reactor at 140°C with 44% o-xylene based on bisphenol A. 20% of the divinyl benzene was charged to the reactor. Then 0.1 wt% based on bisphenol A of 70% methylene sulfonic acid was charged as a catalyst. O-xylene was distilled until clear to remove any water in the system. The remaining divinyl benzene was added over 20 minutes at 150-160°C and then held for 1/2 hour. ⁇ -Methyl styrene was added over 30 minutes at 150-160°C and held for 30 minutes.
  • t-Butyl styrene was added over 30 minutes at 150-160°C and held for 30 minutes.
  • the product was neutralized with 50% KOH and an excess equal to 0.1 % of bisphenol charge (azeotrope H 2 O) was added. After neutralization, the system was placed under vacuum and the ⁇ -xylene recovered from the system to produce a low melting solid (Mp 45-55 °C). Analysis showed the absence of arylolefin and diolefin monomers. No detectable phenol or formaldehyde were found. The product exhibited excellent color, being a very light yellow.
  • Pretteatment of the styrenes and aryldiolefins by passage through at alumina column removed traces of polymerization stabilizers (catechol and hydroquinone). Removal of these color-formers further improved the color performance of these polymers.
  • Example 4 Pretteatment of the styrenes and aryldiolefins by passage through at alumina column removed traces of polymerization stabilizers (catechol and hydroquinone). Removal of these color-formers further improved the color performance of these polymers.
  • the reaction was run in a 1 -liter resin kettle fitted with a stainless steel agitator. The reaction was run under a nitrogen atmosphere to minimize color pickup.
  • Bisphenol A was melted in a reactor at 140°C with 24% ⁇ -xylene based on bisphenol A. 20% of divinyl benzene was charged to the reactor. Then 0.1 wt% based on bisphenol A of 70% methylene sulfonic acid was charged as a catalyst. The remaining divinyl benzene was added over 20 minutes at 150-160°C and then held for 1/2 hour. Next, t-butyl styrene was added at a temperature of 150-160°C over a period of 30 minutes and then held at 150°C for an additional 30 minutes.
  • the reaction was run under a nitrogen atmosphere to minimize color pickup.
  • 15 g of t-butyl phenol was charged into a glass reactor fitted with a magnetic stirring bar and melted at 140 °C.
  • 0.015 g of 70 percent methane sulfonic acid was charged.
  • 10.3 g of 80 percent divinyl benzene was then charged over 5 minutes at 140° C.
  • the reaction was continued at that temperature for an additional 10 minutes.
  • 10 g of /?-t-butyl styrene was charged over 10 minutes and heated for an additional 10 minutes at the 140° C reaction temperature.
  • the mixture was neutralized with an equivalent of diethylene triamine required for the TSA catalyst.
  • the reaction was run under a nitrogen atmosphere to minimize color pickup.
  • 20 g of phenol was charged into a reactor and heated to 140°C.
  • 0.02 grams of methane sulfonic acid (70 percent) was added as a catalyst.
  • 20 g of o- xylene was added as an azeotropic solvent.
  • 25 g ⁇ -methyl styrene was added over 10 minutes at 140°C.
  • the mixture was heated for an additional 20 minutes at 140°C. 6.87 g of 50 percent formaldehyde solution was slowly added allowing water and water of condensation produced by the reaction with the phenolic component to be removed azeotropically over the addition period (20 minutes). After all formaldehyde was added, the mixture was allowed to continue heating for 20 minutes at 140°C.

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Abstract

L'invention concerne la préparation de polymères phénoliques par aralkylation, ces polymères libérant ou émettant des quantités minimales de phénol et de formaldéhyde. Les polymères phénoliques obtenus par aralkylation, selon la présente invention, sont préparés à partir d'un monomère phénolique, d'au moins un dérivé du styrène et d'un composé aryl-dioléfine. En plus de ces composés, on peut ajouter d'autres réactifs pour obtenir un produit avec des propriétés particulières.
PCT/US1996/011223 1995-07-12 1996-07-09 Polymeres phenoliques prepares par des reactions d'aralkylation WO1997003103A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE69617017T DE69617017T2 (de) 1995-07-12 1996-07-09 Phenolische polymere erhalten durch aralkylierung
AT96923613T ATE208798T1 (de) 1995-07-12 1996-07-09 Phenolische polymere erhalten durch aralkylierung
AU64082/96A AU6408296A (en) 1995-07-12 1996-07-09 Phenolic polymers made by aralkylation reactions
EP96923613A EP0837892B1 (fr) 1995-07-12 1996-07-09 Polymeres phenoliques prepares par des reactions d'aralkylation
JP50587297A JP4151748B2 (ja) 1995-07-12 1996-07-09 アラルキル化反応によって製造されたフェノール性ポリマー

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/501,516 1995-07-12
US08/501,516 US5674970A (en) 1995-07-12 1995-07-12 Phenolic polymers made by aralkylation reactions

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WO1997003103A1 true WO1997003103A1 (fr) 1997-01-30

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US (5) US5674970A (fr)
EP (1) EP0837892B1 (fr)
JP (1) JP4151748B2 (fr)
KR (1) KR19990028836A (fr)
CN (1) CN1196069A (fr)
AT (1) ATE208798T1 (fr)
AU (1) AU6408296A (fr)
DE (1) DE69617017T2 (fr)
WO (1) WO1997003103A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5756655A (en) * 1997-01-10 1998-05-26 Georgia-Pacific Resins, Inc. Preparation of phenolic polymers by aralkylation reactions

Families Citing this family (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674970A (en) * 1995-07-12 1997-10-07 Georgia-Pacific Resins, Inc. Phenolic polymers made by aralkylation reactions
US5837798A (en) * 1995-07-12 1998-11-17 Georgia-Pacific Resins Phenolic polymers made by aralkylation reactions
US6127491A (en) * 1995-11-27 2000-10-03 Gerorgia-Pacific Resins, Inc. Phenolic resin polyols and polymers derived from the polyols
ZA9962B (en) * 1998-01-20 1999-07-06 Cook Composites & Polymers Aromatic polyol end-capped unsaturated polyetherester resins and resin compositions containing the same having improved chemical and/or water resistance.
US8177762B2 (en) 1998-12-07 2012-05-15 C. R. Bard, Inc. Septum including at least one identifiable feature, access ports including same, and related methods
US6166151A (en) 1999-06-22 2000-12-26 Georgia-Pacific Resins, Inc. Lactone chain-extended phenolic polyester polyols
US6399740B1 (en) 1999-07-06 2002-06-04 Georgia-Pacific Resins, Inc. Process for reducing mono-functional and non-functional by-products during aralkylation of phenolics
US6350811B1 (en) 2000-01-21 2002-02-26 Arco Chemical Technology, L.P. Aqueous polyurethane dispersions containing phenolic resin moieties
US7671097B2 (en) * 2005-05-24 2010-03-02 Georgia-Pacific Chemicals Llc Stable phenolic resin polymer dispersions having low free aldehyde content
US6245877B1 (en) 2000-04-26 2001-06-12 Arco Chemical Technology, L.P. Urethane compositions
US20020198420A1 (en) * 2001-03-20 2002-12-26 Crompton Corporation. Mono-alkylation process for the preparation of anionic surfactants
US6541673B1 (en) 2001-11-30 2003-04-01 Arco Chemical Technology, L.P. Process for oxyalkylating phenolic compounds
US20050020708A1 (en) * 2002-11-22 2005-01-27 Woodbridge Foam Corporation Foamed isocyanate-based polymer having improved hardness properties and process for production thereof
US20040248996A1 (en) * 2003-06-09 2004-12-09 Crompton Corporation Sodium petroleum sulfonate blends as emulsifiers for petroleum oils
DE102004035157B3 (de) * 2004-07-20 2005-11-17 Clariant Gmbh Mineralöle mit verbesserter Leitfähigkeit und Kältefließfähigkeit
US7947022B2 (en) 2005-03-04 2011-05-24 C. R. Bard, Inc. Access port identification systems and methods
US8029482B2 (en) 2005-03-04 2011-10-04 C. R. Bard, Inc. Systems and methods for radiographically identifying an access port
US9474888B2 (en) 2005-03-04 2016-10-25 C. R. Bard, Inc. Implantable access port including a sandwiched radiopaque insert
US7785302B2 (en) 2005-03-04 2010-08-31 C. R. Bard, Inc. Access port identification systems and methods
US10307581B2 (en) 2005-04-27 2019-06-04 C. R. Bard, Inc. Reinforced septum for an implantable medical device
WO2006116613A1 (fr) 2005-04-27 2006-11-02 C.R. Bard, Inc. Appareils de perfusion
EP3173121B8 (fr) 2005-04-27 2021-03-24 C.R. Bard Inc. Appareils de perfuseur avec septum
US7538162B2 (en) * 2006-06-23 2009-05-26 Bayer Materialscience Llc Process for the production of polyoxyalkylene containing polyols from phenol condensation products
US9265912B2 (en) 2006-11-08 2016-02-23 C. R. Bard, Inc. Indicia informative of characteristics of insertable medical devices
US9642986B2 (en) 2006-11-08 2017-05-09 C. R. Bard, Inc. Resource information key for an insertable medical device
EP2164559B1 (fr) 2007-06-20 2017-10-25 Medical Components, Inc. Orifice d'accès veineux avec indices moulés et/ou radio-opaques
WO2009012395A1 (fr) 2007-07-19 2009-01-22 Innovative Medical Devices, Llc Ensemble orifice d'accès veineux avec indices discernables par rayons x
EP3311877A1 (fr) 2007-07-19 2018-04-25 Medical Components, Inc. Ensemble d'orifice d'accès veineux avec des inscriptions lisibles aux rayons x
US9579496B2 (en) 2007-11-07 2017-02-28 C. R. Bard, Inc. Radiopaque and septum-based indicators for a multi-lumen implantable port
EP2346553B1 (fr) 2008-10-31 2022-01-19 C.R. Bard, Inc. Systèmes et procédés d'identification d'un orifice d'accès
US11890443B2 (en) 2008-11-13 2024-02-06 C. R. Bard, Inc. Implantable medical devices including septum-based indicators
US8932271B2 (en) 2008-11-13 2015-01-13 C. R. Bard, Inc. Implantable medical devices including septum-based indicators
US8715244B2 (en) 2009-07-07 2014-05-06 C. R. Bard, Inc. Extensible internal bolster for a medical device
CN101696266B (zh) * 2009-10-30 2011-06-29 北京师范大学 连苯三酚与二乙烯基苯缩聚树脂的活性醚化物及其合成方法
ES2695907T3 (es) 2009-11-17 2019-01-11 Bard Inc C R Puerto de acceso sobremoldeado que incluye características de anclaje e identificación
US8885299B1 (en) 2010-05-24 2014-11-11 Hutchinson Technology Incorporated Low resistance ground joints for dual stage actuation disk drive suspensions
USD682416S1 (en) 2010-12-30 2013-05-14 C. R. Bard, Inc. Implantable access port
USD676955S1 (en) 2010-12-30 2013-02-26 C. R. Bard, Inc. Implantable access port
WO2014043498A2 (fr) 2012-09-14 2014-03-20 Hutchinson Technology Incorporated Suspensions de lecteur de disque, à actionnement à double étage, basé sur cardan colocalisé
US9586338B2 (en) 2012-10-01 2017-03-07 Georgia-Pacific Chemicals Llc Methods for making lignocellulose containing composite products
US9458298B2 (en) 2012-10-01 2016-10-04 Georgia-Pacific Chemicals Llc Methods for making lignocellulose containing composite products
US8896968B2 (en) 2012-10-10 2014-11-25 Hutchinson Technology Incorporated Co-located gimbal-based dual stage actuation disk drive suspensions with dampers
TWI595019B (zh) * 2012-11-12 2017-08-11 Ｄｉｃ股份有限公司 含有酚性羥基樹脂、環氧樹脂、硬化性樹脂組成物、其硬化物及半導體封裝材料
US8941951B2 (en) 2012-11-28 2015-01-27 Hutchinson Technology Incorporated Head suspension flexure with integrated strain sensor and sputtered traces
US8891206B2 (en) 2012-12-17 2014-11-18 Hutchinson Technology Incorporated Co-located gimbal-based dual stage actuation disk drive suspensions with motor stiffener
US9587077B2 (en) 2013-03-14 2017-03-07 Georgia-Pacific Chemicals Llc Methods for making composite products containing lignocellulose substrates
AU2014244569B2 (en) 2013-03-14 2016-10-06 Georgia-Pacific Chemicals Llc Binder compositions and methods for making and using same
US8896969B1 (en) 2013-05-23 2014-11-25 Hutchinson Technology Incorporated Two-motor co-located gimbal-based dual stage actuation disk drive suspensions with motor stiffeners
US8717712B1 (en) 2013-07-15 2014-05-06 Hutchinson Technology Incorporated Disk drive suspension assembly having a partially flangeless load point dimple
US8896970B1 (en) 2013-12-31 2014-11-25 Hutchinson Technology Incorporated Balanced co-located gimbal-based dual stage actuation disk drive suspensions
US8867173B1 (en) 2014-01-03 2014-10-21 Hutchinson Technology Incorporated Balanced multi-trace transmission in a hard disk drive flexure
CA2944623A1 (fr) 2014-04-02 2015-10-08 Georgia-Pacific Chemicals Llc Procedes de fabrication de produits composites de lignocellulose comportant des liants d'oxydation et un catalyseur metallique complexe
WO2015153520A1 (fr) 2014-04-02 2015-10-08 Georgia-Pacific Chemicals Llc Procédés de fabrication de produits composites à base de lignocellulose au moyen de liants oxydants et catalyseur encapsulé
US9070392B1 (en) 2014-12-16 2015-06-30 Hutchinson Technology Incorporated Piezoelectric disk drive suspension motors having plated stiffeners
US9318136B1 (en) 2014-12-22 2016-04-19 Hutchinson Technology Incorporated Multilayer disk drive motors having out-of-plane bending
US9296188B1 (en) 2015-02-17 2016-03-29 Hutchinson Technology Incorporated Partial curing of a microactuator mounting adhesive in a disk drive suspension
JP6689294B2 (ja) 2015-06-30 2020-04-28 ハッチンソン テクノロジー インコーポレイテッドＨｕｔｃｈｉｎｓｏｎ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｃｏｒｐｏｒａｔｅｄ 金誘電体接合部の信頼性を向上させたディスクドライブヘッドサスペンション構造
US9646638B1 (en) 2016-05-12 2017-05-09 Hutchinson Technology Incorporated Co-located gimbal-based DSA disk drive suspension with traces routed around slider pad
CN109422857A (zh) * 2017-08-30 2019-03-05 北京彤程创展科技有限公司 一种改性双酚酚醛树脂、其制备方法及应用
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US11566170B2 (en) 2018-12-26 2023-01-31 ExxonMobil Technology and Engineering Company Proppant particulates formed from polyaromatic hydrocarbons
CN110643007B (zh) * 2019-11-11 2022-08-02 山东京博木基材料有限公司 一种酚醛树脂木材增韧胶黏剂的制备方法
EP3862376A1 (fr) * 2020-02-07 2021-08-11 Rain Carbon Germany GmbH Agent poisseux pour composés élastomères
CA3217398A1 (fr) 2021-05-11 2022-11-17 Dragan Stojkovic Granules composites de polyolefine-coke utilises comme agent de soutenement pour fracturation hydraulique
WO2024122376A1 (fr) * 2022-12-06 2024-06-13 日本化薬株式会社 Résine époxy, composition de résine durcissable, produit durci et résine phénolique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075771A1 (fr) * 1981-09-25 1983-04-06 Bayer Ag Phénols, leur procédé de synthèse et leur utilisation comme stabilisant de polymère
EP0240762A1 (fr) * 1986-03-13 1987-10-14 Hercules Incorporated Terpolymères terpène-phénol-vinyle aromatiques
JPH06248021A (ja) * 1993-02-25 1994-09-06 Dainippon Ink & Chem Inc ビニル化合物、その製造方法及び精製方法

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2224837A (en) * 1935-04-12 1940-12-10 Ig Farbenindustrie Ag Polymeric product of aromatic hydrocarbons substituted by the ch2=ch-radical
US2687383A (en) * 1949-09-24 1954-08-24 Koppers Co Inc Ion-exchange resins from dihydroxy benzenes or phenol sulfonic acid and polyfunctional unsaturated compounds
US2665312A (en) * 1951-08-03 1954-01-05 Dow Chemical Co Stabilized polyglycol compositions
US2978515A (en) * 1956-05-24 1961-04-04 Goodrich Co B F Process for preparing phenol derivatives
US3004953A (en) * 1959-03-02 1961-10-17 Dow Chemical Co Reaction products of phenols and diisopropenylbenzene
US3177166A (en) * 1961-01-26 1965-04-06 Goodrich Co B F Antioxidants comprising reaction products of liquid rubbers and phenols and compositions containing same
US3328489A (en) * 1963-03-15 1967-06-27 Dow Chemical Co Stabilized polyolefin polymer compositions
US3420915A (en) * 1966-11-17 1969-01-07 Cal Colonial Chemsolve Phenol modified hydrocarbon resins and blends thereof with epoxy resin,polyurethane or polythiol
US3546173A (en) * 1968-04-10 1970-12-08 Du Pont Process for preparing condensates of para-alkyl phenols and divinyl aromatic compounds
US3936510A (en) * 1969-02-17 1976-02-03 Albright & Wilson Limited Cured aromatic resins
DE2027986A1 (de) * 1970-06-06 1971-12-16 Farbenfabriken Bayer AG 5090 Lever kusen Verfahren zur Herstellung von alpha, alpha Bis (hydroxyphenyl) diisopropylben zolen
US3979462A (en) * 1973-04-19 1976-09-07 Bayer Aktiengesellschaft Condensation resins of phenols and α,α'-dihydroxy-diisopropyl benzenes
US3996199A (en) * 1976-02-17 1976-12-07 Dynapol Corporation Oil soluble polymeric antioxidant prepared by condensation of divinylbenzene, hydroxyanisole, tertiary butyl hydroquinone, tertiary butyl phenol and bisphenol A under ortho alkylation conditions
US3996198A (en) * 1975-02-24 1976-12-07 Dynapol One step preparation of linear antioxidant phenolic polymers involving use of impure diolefin feedstock and aluminum catalyst under ortho alkylation conditions
US3996160A (en) * 1975-02-24 1976-12-07 Dynapol Corporation Hydroquinonoid ortho-alkylation polymers and the process of their production
DE2534559A1 (de) * 1975-08-02 1977-02-10 Bayer Ag Verfahren zur herstellung kernalkylierter mehrkernphenole und ihre verwendung
JPS607665B2 (ja) * 1976-01-01 1985-02-26 日石三菱株式会社 硬化性被覆組成物
US4127564A (en) * 1976-06-09 1978-11-28 Dynapol Melt processing recovery of high purity polymeric antioxidants
JPS5952656B2 (ja) * 1977-04-11 1984-12-20 日石三菱株式会社 エポキシ樹脂組成物
US4380554A (en) * 1979-06-25 1983-04-19 Standard Oil Company (Indiana) Polymeric monohydroxybenzenoid hydroquinoid antioxidants
US4310657A (en) * 1979-06-25 1982-01-12 Standard Oil Company (Indiana) Polymeric monohydroxybenzenoid hydroquinoid antioxidants
US4307012A (en) * 1979-12-17 1981-12-22 Standard Oil Company Polymeric alkylbenzenoid hydroquinoid antioxidants
DE3037992C2 (de) * 1980-10-08 1983-04-21 Gesellschaft für Biotechnologische Forschung mbH (GBF), 3300 Braunschweig Verfahren zur Herstellung eines Bindemittels für Holzwerkstoffe
US4403088A (en) * 1982-08-05 1983-09-06 The Goodyear Tire & Rubber Company Plastic resin prepared from meta or para-diisopropenylbenzene and method of preparation
JPS61126162A (ja) * 1984-11-21 1986-06-13 Nippon Oil Co Ltd 熱硬化性樹脂組成物
JPS61145224A (ja) * 1984-12-19 1986-07-02 Hitachi Chem Co Ltd フエノ−ル系重合体の製造法
KR930012016B1 (ko) * 1985-03-26 1993-12-23 도오요오 보오세끼 가부시끼가이샤 고분자형 산화방지제 및 그의 제조방법
US4690995A (en) * 1985-06-06 1987-09-01 The Dow Chemical Company Copolymers containing high concentrations of phenol antioxidant units
US4666974A (en) * 1985-06-06 1987-05-19 The Dow Chemical Company Antioxidant thickening compositions
JPS6245546A (ja) * 1985-08-22 1987-02-27 Hitachi Chem Co Ltd フエノ−ル系重合体の製造方法
US5102962A (en) * 1985-08-22 1992-04-07 Hitachi Chemical Company, Ltd. Phenolic polymer and production thereof
JPS6245658A (ja) * 1985-08-22 1987-02-27 Hitachi Chem Co Ltd 安定化された合成樹脂組成物
US4647952A (en) * 1985-11-13 1987-03-03 The Mead Corporation Phenolic developer resins
JPH01136780A (ja) * 1987-11-24 1989-05-30 Hitachi Chem Co Ltd 新規なフエノール系重合体及びその製造法並びに該重合体を含有する感圧複写紙用顕色剤
IT1223392B (it) * 1987-12-01 1990-09-19 Montedison Spa Procedimento per l'alchilazione di fenoli
US4927905A (en) * 1988-11-14 1990-05-22 The Dow Chemical Company Process for the production of aromatic hydroxyl-containing compound-hydrocarbon resins
EP0506080B1 (fr) * 1991-03-29 1997-02-12 Dainippon Ink And Chemicals, Inc. Durcisseur pour des résines epoxydes et composition de résine époxyde
JPH051131A (ja) * 1991-06-25 1993-01-08 Dainippon Ink & Chem Inc 合成樹脂の製造方法、エポキシ樹脂硬化剤、エポキシ樹脂の製造方法及びエポキシ樹脂組成物
JPH0873570A (ja) * 1994-09-12 1996-03-19 Dainippon Ink & Chem Inc フェノールアラルキル型樹脂の製造方法および硬化性エポキシ樹脂組成物
JP3587570B2 (ja) * 1994-10-20 2004-11-10 三井化学株式会社 ベンジル化ポリフェノール、そのエポキシ樹脂、それらの製造方法および用途
US5674970A (en) * 1995-07-12 1997-10-07 Georgia-Pacific Resins, Inc. Phenolic polymers made by aralkylation reactions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075771A1 (fr) * 1981-09-25 1983-04-06 Bayer Ag Phénols, leur procédé de synthèse et leur utilisation comme stabilisant de polymère
EP0240762A1 (fr) * 1986-03-13 1987-10-14 Hercules Incorporated Terpolymères terpène-phénol-vinyle aromatiques
JPH06248021A (ja) * 1993-02-25 1994-09-06 Dainippon Ink & Chem Inc ビニル化合物、その製造方法及び精製方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 018, no. 639 (C - 1282) 6 December 1994 (1994-12-06) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5756655A (en) * 1997-01-10 1998-05-26 Georgia-Pacific Resins, Inc. Preparation of phenolic polymers by aralkylation reactions
WO1998030616A1 (fr) * 1997-01-10 1998-07-16 Georgia-Pacific Resins, Inc. Preparation de polymeres phenoliques par reactions d'aralkylation

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JP4151748B2 (ja) 2008-09-17
KR19990028836A (ko) 1999-04-15
ATE208798T1 (de) 2001-11-15
US5739259A (en) 1998-04-14
DE69617017T2 (de) 2002-07-04
DE69617017D1 (de) 2001-12-20
CN1196069A (zh) 1998-10-14
US5773552A (en) 1998-06-30
EP0837892A1 (fr) 1998-04-29
JPH11508947A (ja) 1999-08-03
US5756642A (en) 1998-05-26
US5889137A (en) 1999-03-30
US5674970A (en) 1997-10-07
EP0837892B1 (fr) 2001-11-14
AU6408296A (en) 1997-02-10

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